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United States Patent |
5,770,044
|
Ellis
,   et al.
|
June 23, 1998
|
Integrated staged catalytic cracking and hydroprocessing process
(JHT-9614)
Abstract
Disclosed is a catalytic cracking process which includes more than one
catalytic cracking reaction step. The process integrates a hydroprocessing
step between the catalytic cracking reaction steps in order to maximize
olefins production, distillate quality and octane level of the overall
cracked product. Preferably, the hydroprocessing step is included between
the reaction stages, and a portion of the hydroprocessed products, i.e., a
naphtha and mid distillate fraction, is combined with cracked product for
further separation and hydroprocessing. It is also preferred that the
first catalytic cracking reaction step be a short contact time reaction
step.
Inventors:
|
Ellis; Edward S. (Basking Ridge, NJ);
Gupta; Ramesh (Berkeley Heights, NJ);
Bienstock; Martin G. (Succasunna, NJ)
|
Assignee:
|
Exxon Research and Engineering Company (Florham Park, NJ)
|
Appl. No.:
|
702347 |
Filed:
|
August 23, 1996 |
Current U.S. Class: |
208/76; 208/57; 208/72; 208/74; 208/77; 208/78; 208/80; 208/84; 208/100 |
Intern'l Class: |
C10G 051/02 |
Field of Search: |
208/76,72,74,77,78,80,89,100,57
|
References Cited
U.S. Patent Documents
2791541 | May., 1957 | Thompson et al. | 196/49.
|
2953513 | Sep., 1960 | Langer | 208/56.
|
2956003 | Oct., 1960 | Marshall et al. | 208/74.
|
2981674 | Apr., 1961 | Good | 208/70.
|
3896024 | Jul., 1975 | Nace et al. | 208/74.
|
3928172 | Dec., 1975 | Davis et al. | 208/77.
|
4191635 | Mar., 1980 | Quick et al. | 208/89.
|
4551229 | Nov., 1985 | Pecoraro et al. | 208/76.
|
4565620 | Jan., 1986 | Montgomery et al. | 208/80.
|
4585545 | Apr., 1986 | Yancey et al. | 208/74.
|
4606810 | Aug., 1986 | Krambeck et al. | 208/74.
|
5152883 | Oct., 1992 | Melin et al. | 208/61.
|
5582711 | Dec., 1996 | Ellis et al. | 208/76.
|
Primary Examiner: Myers; Helane
Attorney, Agent or Firm: Takemoto; James H.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. Ser. No. 08/292,625,
filed Aug. 17, 1994, and allowed Apr. 29, 1996 U.S. Pat. No. 5,582,711.
Claims
What is claimed is:
1. A catalytic cracking process for producing high quality mid-distillates
comprising the continuous steps of:
(a) contacting a hydrocarbon having an initial boiling point of at least
about 400.degree. F. with cracking catalyst under catalytic cracking
conditions wherein the temperature is from 900.degree. to 1150.degree. F.
and the catalyst contact time is less than 5 seconds forming a first
cracked hydrocarbon product;
(b) conducting the first cracked product to a first separator and
separating from the first cracked hydrocarbon product an overhead naphtha
and light ends fraction and a mid-distillate and gas oil containing
bottoms fraction having an initial boiling point of at least 600.degree.
F.;
(c) conducting the mid-distillate and gas oil containing bottoms fraction
to a hydroprocessor and hydroprocessing the mid-distillate and gas oil
containing bottoms fraction under hydroprocessing conditions forming a
hydroprocessed product;
(d) conducting the hydroprocessed product to a second separator and
separating a light ends and a naphtha fraction, a mid-distillate fraction,
and a hydroprocessed gas oil containing bottoms product;
(e) contacting the hydroprocessed gas oil containing bottoms product with
cracking catalyst under catalytic cracking conditions wherein the
temperature is from 950.degree. to 1250.degree. F. forming a second
cracked hydrocarbon product; and, (f) combining the first cracked
hydrocarbon product and the second cracked hydrocarbon product for
continued separation and hydroprocessing of the mid-distillate and gas oil
containing bottoms fraction.
2. The catalytic cracking process of claim 1, wherein the light ends
fraction is a C.sub.4 - hydrocarbon fraction.
3. The catalytic cracking process of claim 1, wherein less than 50 vol. %
of the first cracked hydrocarbon product formed in step (a) has a boiling
point of less than or equal to 430.degree. F.
4. The catalytic cracking process of claim 1, wherein at least 60 vol. % of
the combined first and second cracked hydrocarbon products have an overall
boiling point of less than or equal to 430.degree. F.
5. The catalytic cracking process of claim 1, wherein the catalytic
cracking conditions of step (e) include a reaction temperature that is at
least equal to that used under the catalytic cracking conditions of step
(a).
6. The catalytic cracking process of claim 1, wherein the hydrocarbon is
contacted with the zeolite catalyst for 1-2 seconds.
7. The catalytic cracking process of claim 1, wherein the hydroprocessor is
a trickle bed, countercurrent, moving bed, expanded bed or slurry bed type
reactor.
8. A catalytic cracking process for producing high quality mid-distillates
comprising continuous steps of:
(a) contacting a hydrocarbon having an initial boiling point of at least
about 400.degree. F. with cracking catalyst under catalytic cracking
conditions wherein the temperature is from 900.degree. to 1150.degree. F.
and the catalyst contact time is less than 5 seconds forming a first
cracked hydrocarbon product;
(b) conducting the first cracked product to a first separator and
separating from the first cracked hydrocarbon product an overhead naphtha
and light ends fraction and a mid-distillate and gas oil containing
bottoms fraction having an initial boiling point of at least 300.degree.
F.;
(c) conducting the mid-distillate and gas oil containing bottoms fraction
to a hydroprocessor and hydroprocessing the mid-distillate and gas oil
containing bottoms fraction under hydroprocessing conditions forming a
hydroprocessed product;
(d) conducting the hydroprocessed product to a second separator and
separating a light ends and a naphtha fraction, a mid-distillate fraction,
and a hydroprocessed gas oil containing bottoms product;
(e) contacting the hydroprocessed gas oil containing bottoms product with
cracking catalyst under catalytic cracking conditions wherein the
temperature is from 950.degree. to 1250.degree. F. forming a second
cracked hydrocarbon product; and
(f) combining the hydroprocessed product from step (c) with the second
cracked hydrocarbon product for continued separation of a light ends and a
naphtha fraction, a mid-distillate fraction, and a hydroprocessed gas oil
containing bottoms fraction wherein the gas oil containing bottoms
fraction is sent for further hydrocracking pursuant to step (e).
Description
FIELD OF THE INVENTION
This invention relates to a staged catalytic cracking process which
includes more than one catalytic cracking reaction step. In particular,
this invention relates to a staged catalytic cracking process which
integrates a hydroprocessing step between the catalytic cracking reaction
steps.
BACKGROUND OF THE INVENTION
Staged catalytic cracking reaction systems have been introduced to improve
the overall octane quality of gasoline. In recent times, however, octane
problems have been minimized and environmental constraints have had a
larger impact on the refiner. As a result, the known staged catalytic
cracking processes are not sufficiently effective in concomitantly meeting
environmental constraints and maintaining a high quality octane gasoline
product.
U.S. Pat. No. 5,152,883 discloses a fluid catalytic cracking unit which
includes two catalytic cracking reaction steps in series. After
hydrocarbon feed is cracked in a first catalytic cracking reaction step,
light hydrocarbon gases and gasoline products are removed from the product
stream and the heavier product portion is hydrotreated. Following
hydrotreating and further gasoline product removal, the heavier
hydrotreated product is cracked in a second catalytic cracking step. The
gasoline products are removed and the heavier products are recycled into
the hydrotreating process.
Rehbein et al., Paper 8 from Fifth World Petroleum Progress, Jun. 1-5,
1959, Fifth World Petroleum Congress, Inc., N.Y., pages 103-122 (which
corresponds to U.S. Pat. No. 2,956,003, Marshall et al.), disclose a two
stage catalytic cracking process which uses a short contact time riser as
the first stage. The first stage is described as being designed to give
40-50 wt. % conversion. The second stage is a dense bed system that is
stated as being designed to charge gas oils from the first stage along
with a recycle stream to give overall conversions of 63-72 wt. %, although
the unit is said to have been run at low enough charge rates to achieve
total conversions from 65-90 wt. %.
As the prior art demonstrates, known catalytic cracking processes which
have been integrated with hydrotreating processes are effective in
significantly increasing the octane level of the gasoline product. The
known systems, however, increase octane by sacrificing the quality of
distillates which can be used as diesel or heating oil. In addition, the
known processes produce a relatively high quantity of light saturated
vapor products as a result of undesirable hydrogen transfer of hydrogen
from the heavier cracked products back to lighter olefin products. By
minimizing the negative effects of this type of hydrogen transfer, a
greater quantity of olefins product can be produced, and these olefins are
made available for further conversion into oxygenates and useful polymer
materials.
Since the products of conventional FCC processes are generally low in
hydrogen content as a result of the relatively low feed hydrogen content
and as a result of conventional FCC operating conditions of high
temperature, (i.e., above 850.degree. F.) and low pressure (i.e., below
about 100 psig), this as noted above favors the formation of olefinic and
aromatic products rather than aliphatic, or hydrogen-rich products. As
recent environmental and regulatory pressures have resulted in
requirements of higher hydrogen content fuels, especially in the diesel
boiling range, a need for hydrogenation of FCC feedstocks and products has
also grown. At the same time, the value of FCC units as producers of
olefinic gases for chemical feedstocks, e.g. propylene and ethylene, has
grown. Hydrogenation technology can be employed to provide enrichment of
the hydrogen content of FCC feeds. However, this hydrogen addition must be
done wisely in order to maximize utilization of the hydrogen that is
consumed and to minimize investment required for the hydrogenation step,
while making the best use of FCC equipment as well. It is, therefore,
desirable to obtain a catalytic cracking process which maximizes olefins
production, distillate quality and octane level.
SUMMARY OF THE INVENTION
In order to overcome problems inherent in the prior art, the present
invention provides a catalytic cracking process comprising the continuous
steps of (a) contacting a hydrocarbon with cracking catalyst under
catalytic cracking conditions forming a first cracked hydrocarbon product;
(b) separating from the first cracked hydrocarbon product a mid-distillate
and gas oil containing bottoms fraction having an initial boiling point of
at least 300.degree. F.; (c) hydroprocessing the middistillate and gas oil
containing bottoms fraction under hydroprocessing conditions forming a
hydroprocessed product; (d) separating a light ends fraction and a naphtha
and mid distillate fraction from the hydroprocessed product, (e)
contacting the separated hydroprocessed product with cracking catalyst
under catalytic cracking conditions forming a second cracked hydrocarbon
product; and, (f) combining the first cracked hydrocarbon product and the
second cracked hydrocarbon product for continued separation and
hydroprocessing of the mid-distillate and gas oil containing bottoms
fraction.
In a preferred embodiment of the invention, the light ends fraction is a
C.sub.4 - hydrocarbon fraction. In addition, the naphtha and mid
distillate fraction is a hydrocarbon distillate fraction having a boiling
point range within C.sub.4 to less than 800.degree. F.
In another preferred embodiment, less than 50 vol. % of the first cracked
hydrocarbon product formed in step (a) has a boiling point of less than or
equal to 430.degree. F. It is further preferred that at least 60 vol. %
preferably at least 75 vol. % of the combined first and second cracked
hydrocarbon products have a boiling point of less than or equal to
430.degree. F.
It yet another preferred embodiment, the catalytic cracking conditions of
step (d) include a reaction temperature that is at least equal to that
used under the catalytic cracking conditions of step (a). More preferably,
the gas oil containing bottoms fraction and the cracking catalyst are
contacted at a temperature which is up to 100.degree. F higher than that
used in step (a). More particularly, the hydrocarbon is contacted with the
cracking catalyst at a temperature of 900.degree.-1150.degree. F.
In still another preferred embodiment, the hydrocarbon in step (a) is
contacted with a zeolite cracking catalyst for less than five seconds.
More preferably, the hydrocarbon is contacted with the zeolite catalyst
for 1-2 seconds.
In yet another preferred embodiment of the invention, the gas oil
containing bottoms fraction and the cracking catalyst are contacted at a
temperature of 950.degree.-1250.degree. F.
BRIEF DESCRIPTION OF THE DRAWING
The present invention will be better understood by reference to the
Detailed Description of the Invention when taken together with the
attached drawing, wherein:
FIG. 1 is a schematic representation of a preferred embodiment of the
invention.
DETAILED DESCRIPTION OF THE INVENTION
Catalytic cracking is a process which is well known in the art of petroleum
refining and generally refers to converting at least one large hydrocarbon
molecule to smaller hydrocarbon molecules by breaking at least one carbon
to carbon bond. For example, a large paraffin molecule can be cracked into
a smaller paraffin and an olefin, and a large olefin molecule can be
cracked into two or more smaller olefin molecules. Long side chain
molecules which contain aromatic rings or naphthenic rings can also be
cracked.
It has been found that the quantity of light olefin product and the quality
of distillate product that is formed during the catalytic cracking process
can be improved by initially incorporating a short contact time reaction
step into the overall catalytic cracking process. After the short contact
time reaction step, a gas oil containing bottoms fraction is separated
from the product portion, and the gas oil containing bottoms fraction is
reprocessed at a higher intensity relative to that used in the short
contact time reaction step.
According to this invention, product yield and quality are further enhanced
by integrating a hydroprocessing step into the staged catalytic cracking
process. Preferably, the hydroprocessing step is included between the
reaction stages.
In essence, the current invention takes advantage of an integration in
which key chemistry synergies between FCC and hydrogenation technologies
are exploited. A first FCC stage is operated at low enough severity,
preferably with short contact time, to achieve high selectivity to olefin
production while preserving sufficient aliphatic character in the
unconverted mid-distillate and bottoms fractions to make acceptable
quality distillate for distillate fuel blendstocks and an acceptable
quality bottoms stream which enables moderate-severity hydroprocessing. At
the same time, the first FCC step accomplishes two important benefits with
respect to subsequent hydroprocessing; the most polar species in the feed
are allowed to deposit on the FCC catalyst, and are subsequently burned
off the FCC catalyst in the regeneration step, providing heat for the
endothermic FCC reactor chemistry. The presence of these polar species
would otherwise result in severe hydroprocessing severity requirements
(i.e., high pressure, large reactor volume) if the feed were
hydroprocessed before the first FCC stage. The second benefit derived from
the first FCC stage is simple volume reduction, that is, in the process of
catalytically cracking the most easily cracked molecules in the FCC feed,
the volume of feedstock remaining to be hydroprocessed is greatly reduced,
and it is reduced to that population of molecules which are not easily
converted in FCC, i.e., those molecules that will most benefit from the
hydroprocessing chemistry which can increase FCC feed crackability. Thus,
the first FCC step selectively prepares a reduced-volume feed to
hydroprocessing which contains a reduced amount of hydroprocessing
catalyst poisons or inhibitors. As a result, the hydroprocessing step can
efficiently be directed to the task of facilitating and enhancing the
selectivity of subsequent FCC conversion.
A novel feature is to include the entire boiling range of unconverted
bottoms from the first FCC step in the feed to the hydroprocessing
reactor, as this bottoms stream, because of the intentional low-intensity
operation of the first FCC stage, is quite suitable as a hydroprocessing
feedstock. As a result of this selective conditioning of the hydrotreater
feed, the hydroprocessing operating severity, e.g., operating pressure and
reactor volume, is much less than would be considered necessary for
hydroprocessing of a conventional FCC bottoms stream. The hydroprocessing
reactor conditions and catalyst can be selected to provide sufficient
hydrogenation and/or hydrocracking to meet a wide range of operating
objectives for the combined FCC-hydrotreating complex. A primary benefit
of the hydroprocessing of the first FCC stage bottoms is to interrupt the
FCC chemistry at the point where there would be a significant decline in
feed crackability upon further FCC processing, and to selectively insert
hydrogen at that point into those unconverted molecules. Then subsequent
FCC reactions can resume with a feedstock of increased crackability. By
splitting the catalytic cracking into two stages, with hydrogen addition
between stages, the right amount of hydrogen can be added to for example
maximize the yield of light olefin species, e.g. butenes, propylene, and
ethylene, in the subsequent FCC stage. With interstage hydroprocessing,
both FCC stages could be operated at short contact times, to maximize
light olefin yield. A related synergy in this approach is that it enables
additional production of higher-hydrogen content mid-distillates, e.g.,
diesel and jet fuel components, by enabling short-contact time catalytic
cracking, which limits hydrogen transfer reactions in the FCC reactor,
that would otherwise increase dehydrogenation of distillates and
hydrogenation of light olefins. Finally, thc second FCC stage can perform
the desired conversion of a reduced volume of more crackable FCC feed from
the hydroprocessing step. Without the interstage hydroprocessing of the
bottoms, the severity required of the second FCC stage would be
considerably higher, greatly reducing flexibility for achieving high
yields of light olefins and high quality distillates, and increasing the
yield of second-stage bottoms byproduct.
The preferred embodiment further optimizes the utilization of the
integrated hydroprocessing step by routing mid-distillate produced in the
catalytic cracking steps to the integrated hydroprocessing unit. As a
result, the desulfurization of diesel product can be accomplished at the
same time that the feed to subsequent FCC is made more crackable via
hydrogenation. The desulfurized mid-distillate can be separated from the
hydroprocessed bottoms via fractionation.
As described herein, a staged catalytic cracking process is a catalytic
cracking process which includes at least two catalytic cracking reaction
steps, preferably performed in series. These reaction steps preferably
take place in a fluid catalytic cracking system, which preferably
comprises two or more main reaction vessels, two are more riser reactors
which connect to one main reaction vessel, or a combination of multiple
risers and reactor vessels.
In the catalytic cracking process of this invention, the hydrocarbon feed
is preferably a petroleum hydrocarbon. The petroleum hydrocarbon is
preferably a hydrocarbon fraction having an initial boiling point of at
least about 400.degree. F., more preferably at least about 600.degree. F.
As appreciated by those of ordinary skill in the art, such hydrocarbon
fractions are difficult to precisely define by initial boiling point since
there is some degree of variability in large commercial processes.
Hydrocarbon fractions which are included in this range, however, are
understood to include gas oils, thermal oils, residual oils, cycle stocks,
topped and whole crudes, tar sand oils, shale oils, synthetic fuels, heavy
hydrocarbon fractions derived from the destructive hydrogenation of coal,
tar, pitches, asphalts, and hydrotreated feed stocks derived from any of
the foregoing.
The hydrocarbon feed is preferably introduced into a riser which feeds a
catalytic cracking reactor vessel. Preferably, the feed is mixed in the
riser with catalytic cracking catalyst that is continuously recycled.
The hydrocarbon feed can be mixed with steam or an inert type of gas at
such conditions so as to form a highly atomized stream of a vaporous
hydrocarbon-catalyst suspension. Preferably, this suspension flows through
the riser into a reactor vessel.
Within the reactor vessel, the catalyst is separated from the hydrocarbon
vapor to obtain the desired products, such as by using cyclone separators.
The separated vapor comprises the cracked hydrocarbon product, and the
separated catalyst contains a carbonaceous material (i.e., coke) as a
result of the catalytic cracking reaction.
The coked catalyst is preferably recycled to contact additional hydrocarbon
feed after the coke material has been removed. Preferably, the coke is
removed from the catalyst in a regenerator vessel by combusting the coke
from the catalyst under standard regeneration conditions. Preferably, the
coke is combusted at a temperature of about 900.degree.-1400.degree. F.
and a pressure of about 0-100 psig. After the combustion step, the
regenerated catalyst is recycled to the riser for contact with additional
hydrocarbon feed. Preferably, the regenerated catalyst contains less than
0.4 wt. % coke, more preferably less than 0.1 wt. % coke.
The catalyst which is used in this invention can be any catalyst which is
typically used to catalytically "crack" hydrocarbon feeds. It is preferred
that the catalytic cracking catalyst comprise a crystalline tetrahedral
framework oxide component. This component is used to catalyze the
breakdown of primary products from the catalytic cracking reaction into
clean products such as naphtha for fuels and olefins for chemical
feedstocks. Preferably, the crystalline tetrahedral framework oxide
component is selected from the group consisting of zeolites,
tectosilicates, tetrahedral aluminophophates (ALPOs) and tetrahedral
silicoaluminophosphates (SAPOs). More preferably, the crystalline
framework oxide component is a zeolite.
Zeolites which can be employed in accordance with this invention include
both natural and synthetic zeolites. These zeolites include gmelinite,
chabazite, dachiardite, clinoptilolite, faujasite, heulandite, analcite,
levynite, erionite, sodalite, cancrinite, nepheline, lazurite, scolecite,
natrolite, offretite, mesolite, mordenite, brewsterite, and ferrierite.
Included among the synthetic zeolites are zeolites X, Y, A, L, ZK-4, ZK-5,
B, E, F, H, J, M, Q, T, W, Z, alpha and beta, ZSM-types and omega.
In general, aluminosilicate zeolites are effectively used in this
invention. However, the aluminum as well as the silicon component can be
substituted for other framework components. For example, the aluminum
portion can be replaced by boron, gallium, titanium or trivalent metal
compositions which arc heavier than aluminum. Germanium can be used to
replace the silicon portion.
The catalytic cracking catalyst used in this invention can further comprise
an active porous inorganic oxide catalyst framework component and an inert
catalyst framework component. Preferably, each component of the catalyst
is held together by attachment with an inorganic oxide matrix component.
The active porous inorganic oxide catalyst framework component catalyzes
the formation of primary products by cracking hydrocarbon molecules that
are too large to fit inside the tetrahedral framework oxide component. The
active porous inorganic oxide catalyst framework component of this
invention is preferably a porous inorganic oxide that cracks a relatively
large amount of hydrocarbons into lower molecular weight hydrocarbons as
compared to an acceptable thermal blank. A low surface area silica (e.g.,
quartz) is one type of acceptable thermal blank. The extent of cracking
can be measured in any of various ASTM tests such as the MAT
(microactivity test, ASTM# D3907-8). Compounds such as those disclosed in
Greensfelder, B. S., et al., Industrial and Engineering Chemistry, pp.
2573-83, November 1949, are desirable. Alumina, silica-alumina and
silica-alumina-zirconia compounds are preferred.
The inert catalyst framework component densifies, strengthens and acts as a
protective thermal sink. The inert catalyst framework component used in
this invention preferably has a cracking activity that is not
significantly greater than the acceptable thermal blank. Kaolin and other
clays as well as .alpha.-alumina, titania, zirconia, quartz and silica are
examples of preferred inert components.
The inorganic oxide matrix component binds the catalyst components together
so that the catalyst product is hard enough to survive interparticle and
reactor wall collisions. The inorganic oxide matrix can be made from an
inorganic oxide sol or gel which is dried to "glue" the catalyst
components together. Preferably, the inorganic oxide matrix will be
comprised of oxides of silicon and aluminum. It is also preferred that
separate alumina phases be incorporated into the inorganic oxide matrix.
Species of aluminum oxyhydroxides-g-alumina, boehmite, diaspore, and
transitional aluminas such as .alpha.-alumina, .beta.-alumina,
.gamma.-alumina, .delta.-alumina, .epsilon.-alumina, .kappa.-alumina, and
.rho.-alumina can be employed. Preferably, the alumina species is an
aluminum trihydroxide such as gibbsite, bayerite, nordstrandite, or
doyelite.
In the staged catalytic cracking process incorporated into this invention,
hydrocarbon feed is subjected to a first catalytic cracking reaction step,
at least a portion of the product of the first reaction step is separated,
and the separated portion is subjected to at least one additional
catalytic cracking reaction step. Separation is preferably achieved using
known distillation methods.
According to this invention, after a hydrocarbon feed undergoes the first
catalytic cracking reaction step, it is preferable to separate a
mid-distillate and gas oil containing bottoms fraction from the product of
the cracking reaction. The mid-distillate fraction preferably has an
initial boiling point of at least about 300.degree. F., more preferably at
least about 350.degree. F. and a final boiling point no more than about
800.degree. F., preferably not more than about 700.degree. F. The gas oil
containing bottoms fraction is preferably a petroleum distillate fraction
having an initial boiling point of at least 600.degree. F., more
preferably at least 650.degree. F. The gas oil containing bottoms fraction
is then used as the feed for at least one subsequent catalytic cracking
reaction step. The remaining product portion of the first catalytic
cracking reaction is sent to storage or subjected to further processing in
other refinery processing units.
It is preferred in this invention that the mid-distillate and gas oil
containing bottoms fraction be hydroprocessed prior to being subjected to
any additional catalytic cracking steps. The mid-distillate and gas oil
containing bottoms fraction is hydroprocessed by passing the fraction over
a hydroprocessing catalyst in the presence of a hydrogen containing gas
under hydroprocessing conditions.
As used herein, hydroprocessing includes both hydrotreating and mild
hydrocracking, with mild hydrocracking indicating that sufficient cracking
of 650.degree. F.+ feed has occurred such that there is a yield of greater
than 15 wt. % and less than 50 wt. % of 650.degree. F.- hydrocarbon
material from the cracking reaction. As is known by those of skill in the
art, the degree of hydroprocessing can be controlled through proper
selection of catalyst as well as by optimizing operation conditions.
It is particularly desirable in this invention that the hydroprocessing
step sufficiently saturate aromatic rings to form more easily crackable
naphthenic rings. It is also desirable that the hydroprocessing step
convert unsaturated hydrocarbons such as olefins and diolefins to
paraffins using a typical hydrogenation catalyst. Objectionable elements
can also be removed by the hydroprocessing reaction. These elements
include sulfur, nitrogen, oxygen, halides, and certain metals.
The hydroprocessing step of the invention is performed under
hydroprocessing conditions. Preferably, the reaction is performed at a
temperature of 400.degree.-900.degree. F., more preferably
600.degree.-850.degree. F. The reaction pressure is preferably 100-3000
psig, more preferably 500-2000 psig. The hourly space velocity is
preferably 0.1-6 V/V/Hr, more preferably 0.3-2 V/V/Hr, where V/V/Hr is
defined as the volume of oil per hour per volume of catalyst. The hydrogen
containing gas is preferably added to establish a hydrogen charge rate of
500-15,000 standard cubic feet per barrel (SCF/B), more preferably
1000-5000 SCF/B.
The hydroprocessing conditions can be maintained by use of any of several
types of hydroprocessing reactors. Trickle bed reactors are most commonly
employed in petroleum refining applications with co-current downflow of
liquid and gas phases over a fixed bed of catalyst particles. It can be
advantageous to utilize alternative reactor technologies.
Countercurrent-flow reactors, in which the liquid phase passes down
through a fixed bed of catalyst against upward-moving treat gas, can be
employed to obtain higher reaction rates and to alleviate aromatics
hydrogenation equilibrium limitations inherent in co-current flow trickle
bed reactors. Moving bed reactors can be employed to increase tolerance
for metals and particulates in the hydrotreater feed stream. Moving bed
reactor types generally include reactors wherein a captive bed of catalyst
particles is contacted by upward-flowing liquid and treat gas. The
catalyst bed can be slightly expanded by the upward flow or substantially
expanded or fluidized by increasing flow rate, for example, via liquid
recirculation (expanded bed or ebullating bed), use of smaller size
catalyst particles which are more easily fluidized (slurry bed), or both.
In any case, catalyst can be removed from a moving bed reactor during
onstream operation, enabling economic application when high levels of
metals in feed would otherwise lead to short run lengths in the
alternative fixed bed designs. Furthermore, expanded or slurry bed
reactors with upward-flowing liquid and gas phases would enable economic
operation with feedstocks containing significant levels of particulate
solids, by permitting long run lengths without risk of shutdown due to
fouling. Use of such a reactor would be especially beneficial in cases
where the feedstocks include solids in excess of about 25 micron size, or
contain contaminants which increase the propensity for foulant
accumulation, such as olefinic or diolefinic species or oxygenated
species. Moving bed reactors which utilize downward-flowing liquid and gas
can also be applied, as they would enable on-stream catalyst replacement.
The catalyst used in the hydroprocessing step can be any hydroprocessing
catalyst suitable for aromatic saturation, desulfurization,
denitrogenation or any combination thereof. Preferably, the catalyst is
comprised of at least one Group VIII metal and a Group VI metal on an
inorganic refractory support, which is preferably alumina or
alumina-silica. The Group VIII and Group VI compounds are well known to
those of ordinary skill in the art and are well defined in the Periodic
Table of the Elements. For example, these compounds are listed in the
Periodic Table found at the last page of Advanced Inorganic Chemistry, 2nd
Edition 1966, Interscience Publishers, by Cotton and Wilkenson.
The Group VIII metal is preferably present in an amount ranging from 2-20
wt. %, preferably 4-12 wt. %. Preferred Group VIII metals include Co, Ni,
and Fe, with Co and Ni being most preferred. The preferred Group VI metal
is Mo which is present in an amount ranging from 5-50 wt. %, preferably
10-40 wt. %, and more preferably from 20-30 wt. %.
All metals weight percents given are on support. The term "on support"
means that the percents are based on the weight of the support. For
example, if a support weighs 100 g, then 20 wt. % Group VIII metal means
that 20 g of the Group VIII metal is on the support.
Any suitable inorganic oxide support material may be used for the catalyst
of the present invention. Preferred are alumina and silica-alumina,
including crystalline alumino-silicate such as zeolite. More preferred is
alumina. The silica content of the silica-alumina support can be from 2-30
wt. %, preferably 3-20 wt. %, more preferably 5-19 wt. %. Other refractory
inorganic compounds may also be used, non-limiting examples of which
include zirconia, titania, magnesia, and the like. The alumina can be any
of the aluminas conventionally used for hydroprocessing catalysts. Such
aluminas are generally porous amorphous alumina having an average pore
size from 50-200 A, preferably, 70-150 A, and a surface area from 50-450
m.sup.2 /g.
In the staged catalytic cracking process of this invention, a short contact
time reaction step is preferably included. In the short contact time
reaction step, it is preferable that the hydrocarbon feed contacts the
cracking catalyst under catalytic cracking conditions to form a first
cracked hydrocarbon product, and the catalytic cracking conditions are
controlled so that less than 50 vol. % of the first cracked hydrocarbon
product has a boiling point below about 430.degree. F. More preferably,
catalytic cracking conditions are controlled so that 25-40 vol. % of the
first cracked hydrocarbon product has a boiling point equal to or below
about 430.degree. F.
The 430.degree. F. boiling point limitation is not per se critical, but is
used to give a general indication of the amount of gasoline and high
quality distillate type products that are formed in the short contact time
reaction step. In the short contact time reaction step, therefore, it is
desirable to initially limit the conversion to gasoline and high quality
distillate type products. By controlling the conversion in this step,
hydrogen transfer can be positively affected in any subsequent cracking
step.
According to this invention, short contact time means that the hydrocarbon
feed will contact the cracking catalyst for less than five seconds. In
typical fluid catalytic cracking systems this means that the vapor
residence time will be less than five seconds. Preferably, in the short
contact time reaction step, the hydrocarbon feed will contact the cracking
catalyst for 1-4 seconds.
The short contact time reaction step can be achieved using any of the known
processes. For example, in one embodiment a close coupled cyclone system
effectively separates the catalyst from the reacted hydrocarbon to quench
the cracking reaction. See, for example, Exxon's U.S. Pat. No. 5,190,650,
of which the detailed description is incorporated herein by reference.
Short contact time can be achieved in another embodiment by injecting a
quench fluid directly into the riser portion of the reactor. The quench
fluid is injected into the appropriate location to quench the cracking
reaction in less than one second. See, for example, U.S. Pat. No.
4,818,372, of which the detailed description is incorporated herein by
reference. Preferred as a quench fluid are such examples as water or steam
or any hydrocarbon that is vaporizable under conditions of injection, and
more particularly the gas oils from coking or visbreaking, catalytic cycle
oils, and heavy aromatic solvents as well as certain deasphalted fractions
extracted with a heavy solvent.
In yet another embodiment, short contact time can be achieved using a
downflow reactor system. In downflow reactor systems, contact time between
catalyst and hydrocarbon can be as low as in the millisecond range. See,
for example, U.S. Pat. Nos. 4,985,136, 4,184,067 and 4,695,370, of which
the detailed descriptions of each are incorporated herein by reference.
The particular catalytic cracking conditions used to achieve conversion to
a product in which less than 50 vol. % of the product has a boiling point
less than 430.degree. F. are readily obtainable by those of ordinary skill
in the art. Once the preferred particular cracking catalyst is chosen, the
operations parameters of pressure, temperature and vapor residence time
are optimized according to particular unit operations constraints. For
example, if it is desired to use a zeolite type of cracking catalyst, the
short contact time reaction step will typically be carried out at a
pressure of 0-100 psig (more preferably 5-50 psig), a temperature of
900.degree.-1150.degree. F. (more preferably 950.degree.-1100.degree. F.)
and a vapor residence time of less than five seconds (more preferably 2-5
seconds).
Regardless of the type of quenching step used to achieve the short contact
time reaction, the catalyst is separated from the vapor to obtain the
desired products according to the known processes, such as by using
cyclone separators. The separated vapor comprises the cracked hydrocarbon
product, and the separated catalyst contains a carbonaceous material
(i.e., coke) as a result of the catalytic cracking reaction.
The products recovered from the short contact time reaction step are
preferably separated so that a mid-distillate and gas oil containing
bottoms fraction is recovered for hydroprocessing and additional cracking.
Preferably, the mid-distillate and gas oil containing bottoms fraction
contains a mid-distillate having an initial boiling point of at least
300.degree. F., more preferably an initial boiling point of at least
350.degree. F.
After the mid-distillate gas oil containing bottoms fraction is separated,
it is preferably hydroprocessed and then separated to recover
hydroprocessed light ends, naphtha and mid-distillate products. The
remaining gas oil containing bottoms is subjected to at least one
subsequent cracking step with a cracking catalyst under catalytic cracking
conditions which favor cracking of the heavier hydrocarbons contained in
the bottoms fraction . It is preferred in any subsequent cracking step
following the hydroprocessing step that the reaction time be longer and
the reaction temperature be at least equal to that used in the short
contact time reaction step. The appropriate catalytic cracking conditions
employed following the short contact time reaction step are preferably
controlled so that the combined products of all of the cracking steps will
yield an overall product in which at least 60 wt. %, preferably at least
75 vol. %, and more preferably at least 85 vol. %, of the overall product
has a boiling point of less than or equal to about 430.degree. F.
In any cracking steps following the hydroprocessing step, the conditions
which are used to achieve the desired overall product boiling point
characteristics are readily obtainable by those of ordinary skill in the
art and are optimized according to the needs of the specific operating
unit. Since the same catalyst is generally used in the short contact time
reaction step as in a subsequent cracking reaction step, it is preferred
to increase slightly the severity of the reaction conditions in the
subsequent reaction step. Preferably, this is done by increasing the
temperature or vapor contact time, or both, in the subsequent reaction
step, while maintaining reaction pressures similar to that in the first
catalytic cracking step, although reaction pressures can be adjusted
without changing temperature or vapor contact time. For example, when
using a zeolite type of cracking catalyst, it is preferred to have a vapor
residence time of less than 10 seconds, more preferably a vapor residence
time of 2-8 seconds.
Depending upon the quality of the feed, severity of hydroprocessing and the
particular reaction equipment used, it can be desirable to increase the
temperature of a subsequent catalytic cracking reaction step. Preferably,
any temperature increase will be less than about 100.degree. F. higher
than in the first catalytic cracking reaction step and in a range of about
950.degree.-1250.degree. F.
Although it is preferred to slightly increase the severity of any cracking
reaction subsequent to the initial short contact time reaction step, this
is not necessary. In general, the more intense the hydroprocessing step,
the less intense can be any subsequent cracking steps.
A preferred embodiment of the invention is shown in FIG. 1 in which the
cracking reaction is carried out using dual risers 10, 11 and a single
reactor 12, with the spent catalyst being regenerated in a single
regenerator 13. Although a dual riser with single reactor design is shown
as onc preferred embodiment, the process of this invention can be carried
out using more than one reactor or more than two risers.
In FIG. 1, fresh hydrocarbon feed is injected into the riser 10 where it
contacts hot catalyst from the regenerator 13. The reaction is preferably
quenched using a cyclone separator 14 to separate the hydrocarbon material
from the spent catalyst. The spent catalyst falls through a stripper and
standpipe and is carried through a return line 15 to the regenerator 13
where it is regenerated for further use.
Cracked hydrocarbon product is removed from the cyclone 14 by way of a line
16 which leads to a separation vessel 17. The separation vessel 17 is used
to separate a mid-distillate and gas oil containing bottoms fraction from
a naphtha and light ends fraction. As stated above, operating conditions
within the riser 10 are maintained such that less than 50 vol. % of the
cracked hydrocarbon product from riser 10 has a boiling point of less than
or equal to 430.degree. F.
The mid-distillate and gas oil containing bottoms fraction is removed from
the separation vessel by way of a line 18. As the mid-distillate and gas
oil containing bottoms fraction is transported through line 18, a hydrogen
containing gas stream is injected at the desired rate, and the entire
mixture is sent to a hydroprocessing reactor 19. The hydroprocessing
reactor 19 contains a hydroprocessing catalyst and the hydroprocessing
reaction is carried out under hydroprocessing conditions, utilizing a
hydroprocessing reactor which contains a fixed or moving bed of
hydroprocessing catalyst.
Following the hydroprocessing reaction, a light ends fraction and a naphtha
and mid-distillate fraction are separated from the hydroprocessed gas oil
containing bottoms product in a separator 20. The light ends fraction is a
C.sub.4 - hydrocarbon fraction, e.g., a hydrocarbon fraction containing
C.sub.4 and lighter hydrocarbons and other gases boiling below about
60.degree. F. including excess hydrogen from the hydroprocessing reaction.
The naphtha fraction includes a hydrocarbon fraction preferably within a
boiling point range of C.sub.4 (about 60.degree. F.) to less than about
430.degree. F. The mid-distillate fraction has a boiling point range of
about 350.degree. F. to less than about 700.degree. F. The separator 20
can be any type of separation equipment capable of effectively separating
the hydroprocessed product into its component parts. For example,
separator 20 can be a simple fractionator or could be a series of
collection vessels such as a hot separator vessel followed by a cold
separator vessel followed by a fractionator.
After separation, the hydroprocessed gas oil containing bottoms fraction is
injected into riser 11 for further catalytic cracking through a line 21. A
portion of the hydroprocessed bottoms can be withdrawn as a purge stream
in a line 23. The cracking reaction in riser 11 is quenched by separating
the cracked products from the spent catalyst using a cyclone separator 22.
The spent catalyst is combined with the spent catalyst that is separated
using the cyclone separator 14, and is sent through the return line 15 to
the regenerator 13 where it is regenerated for further use. The cracked
product is sent to the separator 17 where it is combined with the cracked
product from cyclone separator 14. Alternatively, the cracked product may
be combined with the hydroprocessed product from hydroprocessing reactor
19 and sent to separator 20.
Because the hydroprocessing step removes undesirable contaminants and
improves the quality of the feed to the riser 11, other petroleum
distillate fractions can be combined with the mid-distillate and gas oil
containing bottoms fraction prior to hydroprocessing such as by line 25.
These other petroleum distillate fractions include petroleum fractions
which are generally high in contaminant content, and would not be
typically processed in a catalytic cracking reactor. An example of such
petroleum distillate fractions includes heavy coker oil streams.
Having now fully described this invention, it will be appreciated by those
skilled in the art that the invention can be performed within a wide range
of parameters within what is claimed.
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